A Highly Efficient Gold(I)-Catalyzed Mukaiyama–Mannich Reaction of α-Amino Sulfones with Fluorinated Silyl Enol Ethers To Give β-Amino α-Fluorinated Ketones

◊ These authors contributed equally to this work

Abstract

Ph₃PAuOTf was identified as a powerful catalyst for the ­Mukaiyama–Mannich reaction of fluorinated silyl enol ethers with α-amino sulfones. This provides ready access to β-amino α-fluorinated ketones in good to excellent yields.

Key words

Mukaiyama–Mannich reaction - fluorinated silyl enol ethers - amino sulfones - amino fluorinated ketones - gold catalysis

• References and Notes


For reviews, see:
• 1a Kobayashi S. Mori Y. Fossey JS. Salter MM. Chem. Rev. 2011; 111: 2626
• 1b Kumagai N. Shibasaki M. Bull. Chem. Soc. Jpn. 2015; 88: 503

For reviews of α-amino sulfones:
• 2a Petrini M. Chem. Rev. 2005; 105: 3949
• 2b Monleón A. Synlett 2013; 24: 529

For base-mediated examples, see:
• 3a Weygand F. Steglich W. Oettmeier W. Chem. Ber. 1970; 103: 818
• 3b Mecozzi T. Petrini M. J. Org. Chem. 1999; 64: 8970
• 3c Dahmen S. Bräse S. J. Am. Chem. Soc. 2002; 124: 5940
• 3d Song J. Shih H.-W. Deng L. Org. Lett. 2007; 9: 603
• 3e Palomo C. Oiarbide M. Laso A. López R. J. Am. Chem. Soc. 2005; 127: 17622
• 3f Fini F. Sgarzani V. Pettersen D. Herrera RP. Bernardi L. Ricci A. Angew. Chem. Int. Ed. 2005; 44: 7975 ; and references cited therein

For selected examples of the use of catalytic amounts of Lewis acids:
• 4a Ollevier T. Nadeau E. Eguillon J.-C. Adv. Synth. Catal. 2006; 348: 2080
• 4b Ollevier T. Li Z. Org. Biomol. Chem. 2006; 4: 4440
• 4c Ollevier T. Li Z. Adv. Synth. Catal. 2009; 351: 3251
• 4d Das B. Damodar K. Saritha D. Chowdhury N. Krishnaiah M. Tetrahedron Lett. 2007; 48: 7930
• 4e Kumar RS. C. Reddy GV. Babu KS. Rao JM. Chem. Lett. 2009; 38: 564
• 4f Thirupathi P. Kim SS. Tetrahedron 2010; 66: 8623
• 4g Cao Z.-Y. Zhang Y. Ji C.-B. Zhou J. Org. Lett. 2011; 13: 6398
• 4h Lee S.-H. Kadam ST. Bull. Korean Chem. Soc. 2011; 32: 3738
• 4i Wang Q. Leutzsch M. van Gemmeren M. List B. J. Am. Chem. Soc. 2013; 135: 15334
• 5a Giardinà A. Mecozzi T. Petrini M. J. Org. Chem. 2000; 65: 8277
• 5b Schunk S. Enders D. Org. Lett. 2001; 3: 3177
• 5c Enders D. Oberbörsch S. Synlett 2002; 0471
• 5d Petrini M. Torregiani E. Tetrahedron Lett. 2005; 46: 5999

For a review, see:
• 6a Decostanzi M. Campagne J.-M. Leclerc E. Org. Biomol. Chem. 2015; 13: 7351

For Mannich-type reactions, see:
• 6b Kodama Y. Okumura M. Yanabu N. Taguchi T. Tetrahedron Lett. 1996; 37: 1061
• 6c Jonet S. Cherouvrier F. Brigaud T. Portella C. Eur. J. Org. Chem. 2005; 4304
• 6d Chu L. Zhang X. Qing F.-L. Org. Lett. 2009; 11: 2197
• 6e Yuan Z. Wei Y. Shi M. Chin. J. Chem. 2010; 28: 1709
• 6f Yuan Z. Mei L. Wei Y. Shi M. Kattamuri PV. McDowell P. Li G. Org. Biomol. Chem. 2012; 10: 2509
• 6g Kashikura W. Mori K. Akiyama T. Org. Lett. 2011; 13: 1860

For aldol reactions, see:
• 6h Chorki F. Grellepois F. Crousse B. Ourévitch M. Bonnet-Delpon D. Bégué J.-P. J. Org. Chem. 2001; 66: 7858
• 6i Lefebvre O. Brigaud T. Portella C. J. Org. Chem. 2001; 66: 1941
• 6j Decostanzi M. Godemert J. Oudeyer S. Levacher V. Campagne J.-M. Leclerc E. Adv. Synth. Catal. 2016; 358: 526

For cross-coupling reactions, see:
• 6k Guo Y. Shreeve J.-M. Chem. Commun. 2007; 3583
• 6l Uneyama K. Tanaka H. Kobayashi S. Shioyama M. Amii H. Org. Lett. 2004; 6: 2733

For allylation, see:
• 6m Bélanger É. Cantin K. Messe O. Tremblay M. Paquin J.-F. J. Am. Chem. Soc. 2007; 129: 1034

For reviews, see:
• 7a Pesenti C. Viani F. ChemBioChem 2004; 5: 590
• 7b Liu Y.-L. Yu J.-S. Zhou J. Asian J. Org. Chem. 2013; 2: 194
• 7c Lin J.-H. Xiao J.-C. Tetrahedron Lett. 2014; 55: 6147
• 7d Ni C. Zhu L. Hu J. Acta Chim. Sinica 2015; 73: 90
• 7e Champagne PA. Desroches J. Hamel J.-D. Vandamme M. Paquin J.-F. Chem. Rev. 2015; 115: 9073
• 8a Uoto K. Ohsuki S. Takenoshita H. Ishiyama T. Iimura S. Hirota Y. Mitsui I. Terasawa H. Soga T. Chem. Pharm. Bull. 1997; 45: 1793
• 8b Nakayama K. Kawato HC. Inagaki H. Nakajima R. Kitamura A. Someya K. Ohta T. Org. Lett. 2000; 2: 977
• 8c Cholongitas E. Papatheodoridis GV. Ann. Gastroenterol. 2014; 27: 331
• 9a Liu Y.-L. Zhou J. Chem. Commun. 2012; 48: 1919
• 9b Liu Y.-L. Liao F.-M. Niu Y.-F. Zhao X.-L. Zhou J. Org. Chem. Front. 2014; 1: 742
• 9c Liu Y.-L. Zeng X.-P. Zhou J. Acta Chim. Sinica 2012; 70: 1451
• 9d Yu J.-S. Liu Y.-L. Tang J. Wang X. Zhou J. Angew. Chem. Int. Ed. 2014; 53: 9512
• 9e Liao F.-M. Liu Y.-L. Yu J.-S. Zhou F. Zhou J. Org. Biomol. Chem. 2015; 13: 8906
• 9f Yu J.-S. Zhou J. Org. Biomol. Chem. 2015; 13: 10968
• 9g Yu J.-S. Zhou J. Org. Chem. Front. 2016; 3: 298
• 9h Yu J.-S. Liao F.-M. Gao W.-M. Liao K. Zuo R.-L. Zhou J. Angew. Chem. Int. Ed. 2015; 54: 7381
• 9i Zeng X.-P. Zhou J. J. Am. Chem. Soc. 2016; 138: 8730
• 9j Liao F.-M. Cao Z.-Y. Yu J.-S. Zhou J. Angew. Chem. Int. Ed. 2017; 56: 2459
• 10a Amii H. Kobayashi T. Hatamoto Y. Uneyama K. Chem. Commun. 1999; 1323
• 10b Amii H. Kobayashi T. Terasawa H. Uneyama K. Org. Lett. 2001; 3: 3103
• 10c Huguenot F. Billac A. Brigaud T. Portella C. J. Org. Chem. 2008; 73: 2564
• 10d Prakash GK. S. Hu J. Olah GA. J. Fluorine Chem. 2001; 112: 355

For selected reviews on gold catalysis:
• 11a Hashmi AS. K. Chem. Rev. 2007; 107: 3180
• 11b Bongers N. Krause N. Angew. Chem. Int. Ed. 2008; 47: 2178
• 11c Arcadi A. Chem. Rev. 2008; 108: 3266
• 11d Zhang L. Acc. Chem. Res. 2014; 47: 877
• 11e Fürstner A. Acc. Chem. Res. 2014; 47: 925
• 11f Wei F. Song CL. Ma L. Zhou Y.-D. Tung C.-H. Xu Z.-H. Sci. Bull. 2015; 60: 1479

For selected examples of Au(I) as a σ-Lewis acid catalyst, see:
• 12a Ito Y. Sawamura M. Hayashi T. J. Am. Chem. Soc. 1986; 108: 6405
• 12b Pastor SD. Togni A. J. Am. Chem. Soc. 1989; 111: 2333
• 12c Hayashi T. Kishi E. Soloshonok VA. Uozumi Y. Tetrahedron Lett. 1996; 37: 4969
• 12d Melhado AD. Amarante GW. Wang ZJ. Luparia M. Toste FD. J. Am. Chem. Soc. 2011; 133: 3517
• 12e Lin C.-C. Teng T.-M. Tsai C.-C. Liao H.-Y. Liu R.-S. J. Am. Chem. Soc. 2008; 130: 16417
• 12f Martín-Rodríguez M. Nájera C. Sansano JM. de Cózar A. Cossío FP. Chem. Eur. J. 2011; 17: 14224
• 12g Padilla S. Adrio J. Carretero JC. J. Org. Chem. 2012; 77: 4161
• 12h Zhang M. Yang H. Zhang Y. Zhu C. Li W. Cheng Y. Hu H. Chem. Commun. 2011; 47: 6605
• 12i Jagdale AR. Park JH. Youn SW. J. Org. Chem. 2011; 76: 7204
• 12j Liu B. Li K.-N. Luo S.-W. Huang J.-Z. Pang H. Gong L.-Z. J. Am. Chem. Soc. 2013; 135: 3323
• 12k Shu C. Wang Y.-H. Zhou B. Li X.-L. Ping Y.-F. Lu X. Ye L.-W. J. Am. Chem. Soc. 2015; 137: 9567

For reviews, see:
• 13a Nishizawa M. Imagawa H. Yamamoto H. Org. Biomol. Chem. 2010; 8: 511

For our efforts on Hg(II) catalysis, see:
• 13b Zhou F. Cao Z.-Y. Zhang J. Yang H.-B. Zhou J. Chem. Asian J. 2012; 7: 233
• 13c Cao Z.-Y. Zhou F. Yu Y.-H. Zhou J. Org. Lett. 2013; 15: 42
• 13d Cao Z.-Y. Jiang J.-S. Zhou J. Org. Biomol. Chem. 2016; 14: 5500
• 14 For Au-catalyzed Mannich reactions, see Refs. 12c and 12d.
• 15 Because Bi(OTf)₃ was slightly inferior to Ph₃PAuOTf in terms of the yield of 3a (Table 1), we also examined its performance in other solvents, such as ethyl acetate, toluene, or MeCN, but no better result was obtained (the yields of 3a were 21, 55, and 58%, respectively). When Bi(OTf)₃ was used to mediate the reaction of the aliphatic aldehyde-derived sulfones 1k and 1l, the desired products 3k and 3l were obtained in 15 and 10% yield, respectively, which were much lower than those obtained by using the Au(I) catalyst.
• 16 tert-Butyl (2,2-Difluoro-3-oxo-1,3-diphenylpropyl)carbamate (3a); Typical Procedure Under N₂, a 25 mL dry Schleck tube was charged with Ph₃PAuCl (0.0075 mmol, 3.7 mg) and AgOTf (0.0075 mmol, 1.9 mg), followed by anhyd DCE (2.5 mL). The solution was stirred at r.t. for about 15 min, and then the α-amino sulfone 1a (0.25 mmol) and the fluorinated silyl enol ether 2a (0.375 mmol) were added sequentially. The mixture was stirred at r.t. until 1a was fully converted (TLC), and then purified directly by flash column chromatography to give a white solid; yield: 80.4 mg (89%); mp 136–138 °C. ¹H NMR (300 MHz, CDCl₃): δ = 8.01–7.98 (m, 2 H), 7.65–7.60 (m, 1 H), 7.50–7.45 (m, 2 H), 7.36–7.34 (m, 5 H), 5.62–5.54 (m, 2 H), 1.40 (s, 9 H). ¹⁹F NMR (282 MHz, CDCl₃): δ = –105.86 (d, J _F–F = 275.8 Hz, 1 F), –107.06 (d, J _F–F = 275.2 Hz, 1 F). ¹³C NMR (100 MHz, CDCl₃): δ =188.88 (t, J _C–F = 28.5 Hz), 154.70, 134.37, 133.90, 132.34 (t, J _C–F = 1.9 Hz), 129.83 (t, J _C–F = 3.5 Hz), 128.67, 128.56, 128.36, 116.78 (t, J _C–F = 258.3 Hz), 80.47, 57.08 (t, J _C–F = 24.5 Hz), 28.14.